Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D263/06—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by oxygen atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages

Definitions

• This invention relates to a novel class of N-(substituted) oxazolidines useful as active herbicidal antidotes to protect against and decrease crop injury caused by thiocarbamate and acetanilide herbicides.
• the oxazolidine ring of these antidotes is substituted at the 5-position with a phenyl group which is in turn substituted with one or more alkyl, alkoxy, haloalkyl groups or halogens.
• Other classes of haloacyl oxazolidine herbicide antidotes are known, but none with substituted phenyl groups at the 5-positiaz of the oxazolidine rinq.
• U.S. Patents disclose oxazolidine herbicide antidotes, however, none of such antidotes contain either a substituted or unsubstituted phenyl group at the 5-position of the oxazolidine ring:
• 4,072,688 and 4,322,240 disclose haloacyl oxazolidine herbicidal antidotes wherein an unsubstituted phenyl group is a possible substituent at the 5-positiaz of the oxazolidine ring, and a substituted phenyl is a possible substituent at the 2-position.
• 4,249,931 discloses, among other oxazolidine antidotes, haloacyl oxazolidine antidotes wherein p-chlorophenyl or p-bromophenyl are possible substituents at the 2-positicn of the oxazolidine ring, whereas an alkoxy- or alkylthio- methyl group is a possible substituent at the 5-position.
• U.S. Patent 4,249,932 discloses, among other oxazolidine antidotes, 5-substituted 3-haloacyl oxazolidines, wherein phenoxymethyl is a substituent at the 5-position of the oxazolidine ring.
• An herbicide is a compound which adversely controls or modifies plant growth, e.g., killing, retarding, defoliating, desiccating, regulating, stunting, tillering, stimulating, and dwarfing.
• plant refers to all physical parts of a plant, including seeds, seedlings, saplings; roots, tubers, stems, stalks, foliage, and fruits. "Plant growth” includes all phases of development from seed germination to natural or induced cessation of life.
• Herbicides are generally used to control or eradicate weed pests. They have gained a high degree of commercial success because it has been shown that such control can increase crop yield and reduce harvesting costs. Thiocarbamate and acetanilide herbicides are particularly effective in the control of grassy type weeds which interfere with the cultivation of a wide variety of crops, e.g., barley, corn, cotton, lentils, peanuts, peas, potatoes, soybeans, spinach, tobacco and tomatoes. Frequently the effective use of these herbicides requires the addition of an antidote compound to increase the tolerance of these compounds to the herbicides.
• the most popular methods of herbicide application include: pre plant incorporation into the soil; in-furrow application to seeds and surrounding soil; pre-emergence surface treatment of seeded soil; and post-emergence treatment of the plant and soil.
• a manufacturer of an herbicide generally recommends a range of application rates and concentrations calculated to maximize weed control.
• the range of rates varies from approximately 0.01 to 50 pounds per acre (0.0112 to 56 kilograms per hectare (k/ha)), and is usually in the range of from 0.1 to 25 pounds per acre (0.112 to 28 k / ha).
• the term "herbicidally effective amount” describes the amount of an herbicide compound which controls or modifies plant growth. The actual amount used depends upon several considerations, including particular weed susceptibility and over all cost limitations.
• herbicides damage not only the weeds to be controlled, but to a greater or lesser extent, the desirable cultivated plants as well. This holds true for many herbicidal compounds which have been commercially successful and are commercially available. These herbicides include types such as triazines, urea derivatives, halogenated acetanilides; carbamates, thiocarbamates, thiocarbamate sulfoxides, pyrrolidinones, and the like. Some examples of these compounds are described in U.S. Patent Nos.
• an antidote compound may be a remedy, interferent, protectant, or antagonist.
• antidote describes a compound which has the effect of establishing herbicide selectivity, i.e., continued herbicidal phytotoxicity to weed species and reduced or non-phytotoxicity to cultivated crop species.
• antidotally effective amount describes the amount of an antidote compound which counteracts a phytotoxic response of a beneficial crop to an herbicide.
• N-substituted-5-(substituted phenyl)-1,3-oxazolidines are effective antidotes for the protection of a variety of crops from thiocarbamate and acetanilide herbicide injuries.
• Such antidotal effects as decreasing crop injury and increasing crop tolerance to such herbicides are manifested when such herbicides and antidotes are applied in a variety of ways, for example, independently, or together in tank mixtures or in combination with other compounds.
• N-substituted-5-(substituted phenyl)-1,3- oxazolidines disclosed herein are considered novel and correspond to the following formula: wherein
• Preferred antidotes of this novel class of compounds are the N-haloacyl-5-(substituted phenyl)-1,3-oxazolidines which have acyl groups wherein R is C 1 -C 4 haloalkyl, C 1 -C 4 alkyl, C 1 -C 4 cycloalkyl, C 1 -C 4 haloalkenyl and C 1 -C 4 alkylthio; and phenyl substituents wherein X is C 1 -C 2 alkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkyl, chlorine, bromine or fluorine; and n is 1, 2 or 3.
• R be mono- or di-chloromethyl
• X be para-chloro, para-methyl, meta- or para-methoxy, or meta-trifluoromethyl
• n 1 or 3.
• This invention also embodies a two-part herbicidal system corn- prising
• the preferred thiocarbamates of such compositions are those wherein R 1 and R 3 are C 1 -C 6 alkyl groups and R 2 is either C 1 -C 6 alkyl or C 1 -C 8 cycloalkyl.
• the most preferred thiocarbamates are S-propyl N,N-dipropyl thiocarbamate; S-ethyl N,N-dipropyl thiocarbamate; S-ethyl N,N-diisobutyl thiocarbamate; and S-ethyl-N-ethyl-N-cyclohexyl thiocarbamate.
• compositions including thiocarbamates are delineated above in the discussion of the novelty of the instant compounds.
• the invention also embodies a two-part herbicidal system comprising
• the preferred acetanilides of such composition are those wherein R 4 and R 6 are each independently alkyl having 1-4, or more preferably 1-2, carbon atoms, inclusive; and R 5 is alkoxyalkyl having 1-4 carbon atoms, inclusive.
• the active acetanilide compounds employed in the invention may include: 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide; 2-chloro-2'-methyl-6'-ethyl-N-(2-methoxypropyl)-acetanilide; 2-chloro-2',6'-dimethyl-N-(methoxyethyl) acetanilide; 2-chloro-2'-methyl-6'-ethyl-N-(ethoxymethyl) acetanilide; 2-chloro-N-isopropyl acetanilide; 2-chloro-2',6'-diethyl-N-(n-butoxymethyl) acetanilide; 2-chloro-N-carbethoxymethyl-2',6'-diethyl acetanilide; and 2-chloro-2'-methyl-6'-ethyl-(2-methoxy-1-methyle
• acetanilides of such compositions are 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide and 2-chloro-2',6'dimethyl-N-(methoxymethyl) acetanilide.
• the most preferred antidote of such acetanilide/antidote composition is 2,2-dimethyl-3-(dichloroacetyl)-5-(p-methoxyphenyl)-1,3-oxazolidine.
• This invention also relates to a method of controlling undesirable vegetation and reducing crop injury caused by thiocarbamate and acetanilide herbicides which comprises applying to the locus where control is desired a compound of the formula wherein
• the locus where control and herbicidal crop injury reduction is desired may include soil, seeds, seedlings and vegetation.
• the active antidote compounds of the present invention can be prepared by the following methods.
• TMSCN trimethylsilyl cyanide
• oxazolidine intermediates are prepared by condensing the amino alcohol with dimethyl ketone in boiling toluene with the continuous separation of water. This method is essentially described by Bergmann et al., J.A.C.S., 75:385 (1953). Aliquots of these solutions are then used to prepare the copounds of this invention.
• the oxazolidine intermediate is then reacted with the appropriate acid halide in the presence of a hydrogen halide acceptor, such as triethylamine, to produce the desired N-haloacyl-5-(substituted phenyl) oxazolidine.
• a hydrogen halide acceptor such as triethylamine
• the reaction mixture was then allowed to stand for two days at room temperature. An additional 3 ml of TMSCN and a trace of triphenylphosphine was then added to the mixture. For two hours, the mixture was heated to maintain a temperature range of 70-80°C. Two ml of TMSCN was added, and the temperature was raised to 130-140°C and maintained for another 2.5 hours. The g.c. area percent was 99%. The reaction mixture was evaporated in vacuo. The product was a red-yellow liquid. The yield was 22.7 g (96.6%). The IR and NMR spectra were consistent with the expected structure.
• the structure of the expected product was confirmed by an NMR spectrum. It was a waxy solid with a g.c. area percent of 94.5%. The yield was 5.3 g (57.6%).
• the product had a melting point of 95-100.C.
• the yield was 4.2 g (65.1%).
• the structure was confirmed by IR and NMR spectra.
• the product was a tan solid with a melting point between 105-107°C.
• the yield was 4.4 g (83.3%).
• the structure was confirmed by IR spectrun.
• the herbicide was either incorporated into the soil prior to planting or applied to the soil after planting and prior to emergence of the plants. In some cases of pre-plant incorporation, the herbicide was incorporated into the soil alone in preparation for in-furrow application of the antidote; in others the herbicide solution was tankmixed with the antidote solution prior to incorporation.
• the antidote solutions were applied to the soil either by in-furrow surface application or by pre-plant incorporation. In all cases of pre-plant incorporation, the antidote was tank-mixed with the herbicide prior to incorporation into the soil. These methods are abbreviated in the tables as follows:
• a one pint (473 cubic centimeter (cc)) sample of soil containing the previously incorporated herbicide was removed and retained from each planting flat. After leveling and furrow- inq the soil, seeds of the crop or weed species were planted 1/2 inch deep (1.27 centimeter). Each flat was divided in half by a wooden barrier. A stock solution of the antidote was atanized directly onto the exposed seeds and soil in the open furrow on one side of the barrier. The seeds in the entire flat were then covered with the previously removed soil. The antidotally untreated sections of flats were compared for observed differences which would indicate lateral movement of the antidote through the soil.
• Control flats contained crops treated with herbicide only.
• All of the soil used in the tests described herein was loamy sand soil treated with 50 parts per million (ppm) each of a comnercially available fungicide, N-[(trichloromethyl)-thio]-4-cyclohexene-1,2-dicarboximide, and 17-17-17 fertilizer, which contains 17% by weight equivalent each of nitrogen, phosphorus pentoxide, and potassium oxide.
• the treated crops initially screened for diminution of herbicidal injury were milo, wheat (WHT), cotton (COT), rice, barley (BAR), corn and soybeans (SOY).
• WHT wheat
• cotton cotton
• BAR barley
• SOY corn and soybeans
• the compound was also tested on the following weeds: watergrass (WG) (Echinochloa crusgalli); foxtail (FT) (Stearia viridis); wild oats (WO) (Avena fatua); and shattercane (SC) (Sorghum bicolor).
• the results are indicated in Tables III and IV by numbers separated by slashes, for eg., *10/65.
• the first number is the percentage of injuries sustained by the indicated crop or weed species when treated by both the antidote and herbicide at the rates specified.
• the second number is the percentage of injuries sustained by the crop or weed species when treated by the herbicide alone at the rate specified.
• the numbers represent: Antidote treated/Antidote untreated.
• the injury to the crop (Table III) or weeds (Table IV) is shown as a percentage of damage done to the plants as compared to an evaluation of the overall undamaged state of the plants indicated by check flats not treated with either herbicide or antidote.
• the damage done to the plants is a function of the number of plants injured and the extent of injury to each plant. This rating is made four (4) weeks after application of the herbicide alone or of the herbicide in combination with the antidote.
• Table IV shows that the antidote compound has no effect on weeds, i.e., herbicidal injury to the weeds is sustained even in the presence of an antidote compound.
• the compounds of this invention show good antidotal activity with a variety of crops, especially with milo and corn. Use of the antidote compounds, as indicated in Table IV, did not result in a reduction of herbicidal injury to weeds.
• a formulation is the incorporation of a formulant in a form which is directly usable on crops and weeds.
• a "formulant" is the material which is to be formulated.
• the formulant may be either an antidote compound alone or an herbicide and antidote ccmposi- tion.
• the purpose of the formulation is to apply the formulant to the locus where it is desired to establish herbicidal selectivity by a convenient method.
• the "locus” may include soil, seeds, seedlings and veqeta- tion.
• the formulations are commonly dusts, wettable powders, granules, solutions or emulsifiable concentrates.
• Dusts are free-flowing powder compositions containinq the formulant impregnated on a particulate carrier.
• the particle size of the carriers is usually in the approximate range of 30 to 50 microns.
• suitable carriers are talc, bentonite, diatomaceous earth, and pyro- phyllite.
• the composition generally contains up to 50% of formulant.
• Anti-caking and anti-static agents may also be added. Dusts may be applied by spraying from boom and hand sprayers on airplanes.
• Wettable powders are finely divided compositions comprising a particulate carrier impregnated with the formulant and additionally containing one or more surface active agents.
• the surface active agent promotes rapid dispersion of the powder in an aqueous medium to form stable, sprayable suspensions.
• a wide variety of surface active a q ents can be used, for example, long chain fatty alcohols and alkali metal salts of the sulfated fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omega-substituted polyethylene glycols of relatively long chain length.
• a list of surface active agents suitable for use in aqriculture formulations can be found in Wade Van Valkenburg, Pesticide Formulations (Marcel Dekker, Inc., N.Y., 1973) at pages 79-84.
• Granules comprise the formulant impregnated on a particulate inert carrier having a particle size of about 1 to 2 millimeters (nm) in diameter.
• the granules can be made by spraying a solution of the formulant in a volatile solvent onto the granular carrier.
• suitable carriers for the preparation of granules include clay, vermiculite, sawdust, and granular carbon.
• Emulsifiable concentrates consist of an oil solution of the formulant plus an emulsifying agent. Prior to use the concentrate is diluted with water to form a suspended emulsion of oil droplets.
• the emulsifiers used are usually a mixture of anionic and nonionic surfactants.
• Other additives, such as suspending agents and thickeners, may be included in the emulsifiable concentrate.
• the proportion of antidote compound to herbicide compound generally ranges from approximately 0.001 to 30 parts by weight of the antidote compound per weight of the herbicide compound.
• formulations generally contain several additives in addition to the formulant and carrier or agent.
• inert ingredients e.g., inert ingredients, diluent carriers, organic solvents, water, oil and water, water in oil emulsions, carriers of dusts and granules, and surface active wetting, dispersing and emulsifying agents.
• Fertilizers e.g., ammonium nitrate, urea and superphosphate, may be included.
• Aids to rooting and qrowth e.g., compost, manure, humus and sand, may also be included.
• the antidote compounds and herbicide and antidote compositions of this invention can be applied to a crop by addition of the formulant to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed.
• the formulant can be applied to the soil in the form of a solution in a suitable solvent.
• Solvents frequently used in these formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene and aromatic petroleun fractions rich in methylated naphthalenes.
• Liquid solutions, like dusts, may be applied by spraying from bean and hand sprayers on airplanes.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Environmental Sciences (AREA)
• Dentistry (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Toxicology (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Catching Or Destruction (AREA)

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Cited By (6)

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• 1984
  • 1984-08-03 PL PL1984249318A patent/PL144076B1/pl unknown
  • 1984-08-09 EP EP84305427A patent/EP0136016A3/de not_active Withdrawn
  • 1984-08-17 TR TR5516A patent/TR22507A/xx unknown
  • 1984-08-21 RO RO84115545A patent/RO89179A/ro unknown
  • 1984-08-22 DD DD84266528A patent/DD231978A5/de not_active IP Right Cessation
  • 1984-08-22 IL IL72750A patent/IL72750A0/xx unknown
  • 1984-08-22 CS CS846357A patent/CS243494B2/cs unknown
  • 1984-08-23 ZA ZA846567A patent/ZA846567B/xx unknown
  • 1984-08-23 PT PT79120A patent/PT79120B/pt unknown
  • 1984-08-23 HU HU843175A patent/HUT34739A/hu unknown
  • 1984-08-23 AU AU32316/84A patent/AU568565B2/en not_active Ceased
  • 1984-08-24 JP JP59175297A patent/JPS6072871A/ja active Pending
  • 1984-08-24 BG BG078446A patent/BG44371A3/xx unknown
  • 1984-08-24 BG BG066701A patent/BG43682A3/xx unknown
  • 1984-08-24 DK DK405484A patent/DK405484A/da not_active Application Discontinuation
  • 1984-08-24 KR KR1019840005155A patent/KR850001668A/ko not_active Abandoned
  • 1984-08-24 BR BR8404253A patent/BR8404253A/pt unknown
  • 1984-08-24 ES ES535402A patent/ES8604176A1/es not_active Expired

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